CN103663393B - The preparation method of two fluoro sulfimide lithium - Google Patents
The preparation method of two fluoro sulfimide lithium Download PDFInfo
- Publication number
- CN103663393B CN103663393B CN201210331995.0A CN201210331995A CN103663393B CN 103663393 B CN103663393 B CN 103663393B CN 201210331995 A CN201210331995 A CN 201210331995A CN 103663393 B CN103663393 B CN 103663393B
- Authority
- CN
- China
- Prior art keywords
- lithium
- fluoro
- preparation
- carbonate
- fluoro sulfimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to the preparation method of a kind of pair of fluoro sulfimide lithium, described method comprises: in unsaturated carbonate alkyl ester and/or saturated fluoro alkyl carbonate solvent, under the catalytic condition of the crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd, two chlorosulfonyl imine lithium is reacted with the alkaline metal fluoride cpd as fluorizating agent, obtains two fluoro sulfimide lithium.Preparation method's operational path of of the present invention pair of fluoro sulfimide lithium is simple, easily realizes preparation of industrialization.
Description
Technical field
The present invention relates to the preparation method of a kind of pair of fluoro sulfimide lithium.
Background technology
Two fluoro sulfimide lithium of indication of the present invention are the compounds with following structure:
Two fluoro sulfimide lithium can be used for multiple fields, can be used as lithium-ion battery electrolytes additive, improves cycle performance of lithium ion battery, also can use as primary cell ionogen; Can be used as polymerisation catalysts; Also can be used for static inhibitor in industrial circle to use.
Present research shows, two fluoro sulfimide lithium is applied in the electrolytic solution of chargeable lithium cell, effectively can reduce the SEI layer high/low temperature resistance be at low temperatures formed on electrode plate surface, reduce the capacitance loss of lithium cell in put procedure, thus high-capacity battery is provided, improve the chemical property of battery.
The technology of preparing of two fluoro sulfimide lithium, having appeared in the newspapers both at home and abroad, to be mainly two chlorosulfonyl imines be that raw material and fluosulfonic acid react, obtain two fluoro sulfimide, two fluoro sulfimide lithium is obtained by reacting again with lithium salts, and Beran etc. proposes with lithium perchlorate to be that raw material carries out replacement(metathesis)reaction with two fluoro sulfimide potassium, obtains two fluoro sulfimide lithium product salt.US Patent No. 7253317 synthesizes two fluoro sulfimide alkali metal salt with alkaline metal fluoride cpd and two chlorosulfonyl imines in Nitromethane 99Min., containing impurity such as a chlorine one fluoro sulfimide, fluoro sulphonamide in product, be difficult to be separated, yield is low, is difficult to obtain solid-state salt simultaneously.All also exist in above operational path that operational path is long, product composition is complicated and carry impurity secretly in product is not easy the shortcomings such as separation further as acid esters or potassium plasma content, also have impact on the industrializing implementation of product further.
The present invention is directed to above shortcoming, directly with two chlorosulfonyl imine lithium for raw material, under catalyzer and suitable solvent, direct and alkaline metal fluoride cpd carries out the exchange of fluorine chlorine, obtain solid-state two fluoro sulfimide lithium, in product, fluorine, chlorine and potassium plasma content are all at below 10ppm, reach the material requirements of application lithium battery electrolytes completely, operational path is simple simultaneously, easily realizes preparation of industrialization.
Summary of the invention
The present inventor is for problems of the prior art, a kind of novel process being suitable for preparing two fluoro sulfimide lithium has been found: take two chlorosulfonyl imine lithium to be raw material after further investigation, under suitable catalysts and solvents, directly carry out the exchange of fluorine chlorine with alkaline metal fluoride cpd, obtain two fluoro sulfimide lithium product.Compared with technique general in the world at present, the operational path of preparation method of the present invention is simple and easy to control, and the impurity such as the fluorine carried secretly in product, chlorine and alkalimetal ion, all lower than 100ppm, even lower than 10ppm, meet electronic-grade application requiring.
On the one hand, the invention provides the preparation method of a kind of pair of fluoro sulfimide lithium, described method comprises: in unsaturated carbonate alkyl ester and/or saturated fluoro alkyl carbonate solvent, under the catalytic condition of the crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd, two chlorosulfonyl imine lithium is reacted with the alkaline metal fluoride cpd as fluorizating agent, obtains two fluoro sulfimide lithium.
Wherein, the structural formula of described pair of chlorosulfonyl imine lithium is:
The structural formula of described pair of fluoro sulfimide lithium is:
In one embodiment of the present invention, described alkaline metal fluoride cpd is selected from lithium fluoride, Potassium monofluoride, Sodium Fluoride or their mixture, and the add-on of this alkaline metal fluoride cpd is 2.01 ~ 10 times of two chlorosulfonyl imine lithium mole number.
In a preferred embodiment of this invention, described unsaturated carbonate alkyl ester solvents be selected from methylcarbonate, diethyl carbonate, dipropyl carbonate, Methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, in one or more mixture, its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium massfraction.
In a preferred embodiment of this invention, described saturated fluoro alkyl carbonate solvent is selected from one or more the mixture in trifluoroethyl ethyl carbonate ester, two trifluoroethyl carbonic ether, trifluoroethyl methyl carbonic, and its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium mass fraction.
In a preferred embodiment of this invention, the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is 12-crown-4 (lithium fluoride), 15-is preced with-5 (Sodium Fluorides) or 18-is preced with-6(Potassium monofluoride).
In a preferred embodiment of this invention, the add-on of described crown ether-like phase transfer catalysts is 0.1% ~ 10% of two chlorosulfonyl imine lithium massfraction.
In one embodiment, reaction of the present invention is carried out at the temperature of 40 ~ 130 DEG C, and the reaction times is 8 ~ 24 hours.
Specifically, the invention provides the preparation method of a kind of pair of fluoro sulfimide lithium, described method comprises: in unsaturated carbonate alkyl ester and/or saturated fluoro alkyl carbonate solvent solvent, under the catalytic condition of the crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd, two chlorosulfonyl imine lithium is reacted with the alkaline metal fluoride cpd as fluorizating agent, obtains two fluoro sulfimide lithium.
In the present invention, described reaction formula is as follows:
Wherein, R is selected from one or more in lithium, potassium, sodium.
In the present invention, described alkaline metal fluoride cpd RF is selected from lithium fluoride, Potassium monofluoride, Sodium Fluoride or their mixture, and the add-on of this alkaline metal fluoride cpd is 2.01 ~ 10 times of two chlorosulfonyl imine lithium mole number.
In an embodiment of the invention, described unsaturated carbonate alkyl ester solvents is selected from one or more the mixture in methylcarbonate, diethyl carbonate, dipropyl carbonate, Methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, and its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium massfraction.
In another embodiment of the present invention, described saturated fluoro alkyl carbonate solvent is selected from one or more the mixture in trifluoroethyl ethyl carbonate ester, two trifluoroethyl carbonic ether, trifluoroethyl methyl carbonic, and its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium mass fraction.
In the present invention, described unsaturated carbonate alkyl ester solvents can mix with saturated fluoro alkyl carbonate solvent, as the solvent used in the present invention's reaction.
In the present invention, the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is preferably 12-crown-4 (lithium fluoride), 15-is preced with-5 (Sodium Fluorides) or 18-is preced with-6(Potassium monofluoride).Namely, the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd preferably adapts with lithium fluoride 12-crown-4 phase-transfer catalyst, the 15-that adapts with Sodium Fluoride are preced with-5 phase-transfer catalysts or are preced with-6 phase-transfer catalysts with the 18-that Potassium monofluoride adapts.
In this article, described 12-crown-4 (lithium fluoride) refers to that the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is 12-crown-4 when the alkaline metal fluoride cpd used is for lithium fluoride.Similar, described 15-is preced with-5 (Sodium Fluorides) and refers to that the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is that 15-is preced with-5 when the alkaline metal fluoride cpd used is for Sodium Fluoride.Described 18-is preced with-6(Potassium monofluoride) refer to that the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is that 18-is preced with-6 when the alkaline metal fluoride cpd used is for lithium fluoride.
In the present invention, the add-on of described crown ether-like phase transfer catalysts is 0.1% ~ 10% of two chlorosulfonyl imine lithium massfraction.
In the present invention, described reaction is carried out at the temperature of 40 ~ 130 DEG C, and the reaction times is 8 ~ 24 hours.
In the present invention, object of the present invention is particular by realize with under type:
With two chlorosulfonyl imine lithium for raw material, alkaline metal fluoride cpd is fluorination reagent, in unsaturated carbonate alkyl ester and/or saturated fluoro alkyl carbonate solvent solvent, with the crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd for catalyzer, react at a certain temperature, obtain containing two fluoro sulfimide lithium product.
Described alkaline metal fluoride cpd is selected from one or more the mixture in lithium fluoride, Sodium Fluoride, Potassium monofluoride, and its add-on is 2.01 ~ 10 times of two chlorosulfonyl imine lithium mole number.
Described unsaturated carbonate alkyl ester solvents is selected from one or more the mixture in methylcarbonate, diethyl carbonate, dipropyl carbonate, Methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, and its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium massfraction.
In the present invention, described unsaturated carbonate alkyl ester solvents can also be the solvent based on unsaturated carbonate alkyl ester, it is specific non-proton mixed solvent, be selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, two trifluoroethyl carbonic ether, trifluoroethyl methyl carbonic, acetonitrile, tetrahydrofuran (THF) more than two kinds mixtures, add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium mass fraction.
In addition, the described solvent based on unsaturated carbonate alkyl ester is the solvent based on saturated fluoro alkyl carbonate, be selected from one or more the mixture in trifluoroethyl ethyl carbonate ester, two trifluoroethyl carbonic ether, trifluoroethyl methyl carbonic, its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium mass fraction.
The described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is 12-crown-4-ether (lithium fluoride), 15-is preced with-5-ether (Sodium Fluoride) and/or 18-is preced with-6-ether (Potassium monofluoride)
In the present invention, the add-on of described crown ether-like phase transfer catalysts is 0.1% ~ 10% of the two chlorosulfonyl imine lithium massfraction of raw material.
In the present invention, the temperature of described reaction is 40 ~ 130 DEG C, and the reaction times is 8 ~ 24 hours.
Compared with existing preparation method, the present invention has the following advantages:
1. operational path is simple and easy to control;
2. easily purify, fluorine residual in product and chlorine equal size low, constant product quality;
3. yield is high, and product purity high (>=99.9%), can meet electronic-grade requirement.
Accompanying drawing explanation
Fig. 1 is that the two fluoro sulfimide of the present invention detects the collection of illustrative plates obtained through fourier infrared.
Embodiment
Following the present invention will be described in further detail in conjunction with specific embodiments, make technician clearly understand advantage of the present invention.Should be appreciated that, content wherein just with explaining, and is construed as limiting protection scope of the present invention absolutely not.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or carry out according to the condition that manufacturer advises.Unless otherwise indicated, all numbers are parts by weight, and all per-cent is weight percentage meter.
embodiment 1
220.0g(1mol is added under nitrogen protection in 1000ml there-necked flask) two chlorosulfonyl imine lithium, 220.0g methylcarbonate, 52.26g (2mol) lithium fluoride and 0.22g 12-crown-4-ether.Under agitation, react after 8 hours at 40 DEG C and be cooled to room temperature, filter, obtain white crystal 149g after filtrate steaming removal solvent, yield 79.7%.The logical 848 potentiometric titrator chlorine detection content of Switzerland ten thousand are adopted to be 7ppm.Product detects through fourier infrared, at 1401cm
-1, 1386cm
-1, 1190cm
-1, 1225cm
-1, 859cm
-1, 845cm
-1, 783cm
-1, 747cm
-1, by two fluoro sulfimide standard spectrogram contrast, be defined as the characteristic group of two fluoro sulfimide.
embodiment 2
220.0g(1mol is added under nitrogen protection in 3000ml there-necked flask) two chlorosulfonyl imine lithium, 2200.0g diethyl carbonate, 420.0g (10mol) Sodium Fluoride and 22g 15-are preced with-5-ether.Under agitation, react after 24 hours at 100 DEG C and be cooled to room temperature, filter, obtain white crystal 155g after filtrate steaming removal solvent, yield 82.9%.The logical 848 potentiometric titrator chlorine detection content of Switzerland ten thousand are adopted to be that 5ppm, Shimadzu AA-6300 atomic absorption instrument detects sodium ion 0.7ppm.Detect, at 1401cm through fourier infrared
-1, 1386cm
-1, 1192cm
-1, 1226cm
-1, 859cm
-1, 845cm
-1, 783cm
-1, 747cm
-1, by two fluoro sulfimide standard spectrogram contrast, be defined as the characteristic group of two fluoro sulfimide.
embodiment 3
220.0g(1mol is added under nitrogen protection in 1000ml there-necked flask) two chlorosulfonyl imine lithium, 200.0g diethyl carbonate and 200g dipropyl carbonate, 290.0g (5mol) Potassium monofluoride and 22g 18-are preced with-6-ether.Under agitation, react after 14 hours at 130 DEG C and be cooled to room temperature, filter, obtain white crystal 153g after filtrate steaming removal solvent, yield 81.8%.The logical 848 potentiometric titrator chlorine detection content of Switzerland ten thousand are adopted to be that 2ppm, Shimadzu AA-6300 atomic absorption instrument detects sodium ion potassium ion 0.2ppm.Detect, at 1401cm through fourier infrared
-1, 1386cm
-1, 1190cm
-1, 1225cm
-1, 859cm
-1, 845cm
-1, 783cm
-1, 747cm
-1, by two fluoro sulfimide standard spectrogram contrast, be defined as the characteristic group of two fluoro sulfimide.
embodiment 4
220.0g(1mol is added under nitrogen protection in 1000ml there-necked flask) two chlorosulfonyl imine lithium, the two trifluoroethyl carbonic ether of 400.0g, 290.0g (5mol) Potassium monofluoride and 22g 18-are preced with-6-ether.Under agitation, react after 24 hours at 110 DEG C and be cooled to room temperature, filter, obtain white crystal 156g after filtrate steaming removal solvent, yield 83.4%.The logical 848 potentiometric titrator chlorine detection content of Switzerland ten thousand are adopted to be that 5.1ppm, Shimadzu AA-6300 atomic absorption instrument detects sodium ion potassium ion 0.6ppm.Detect, at 1401cm through fourier infrared
-1, 1386cm
-1, 1190cm
-1, 1225cm
-1, 859cm
-1, 845cm
-1, 783cm
-1, 747cm
-1, by two fluoro sulfimide standard spectrogram contrast, be defined as the characteristic group of two fluoro sulfimide.
embodiment 5
220.0g(1mol is added under nitrogen protection in 1000ml there-necked flask) two chlorosulfonyl imine lithium, the two trifluoroethyl carbonic ether of 200.0g and 200.0g acetonitrile, 290.0g (5mol) Potassium monofluoride and 22g 18-are preced with-6-ether.Under agitation, react after 24 hours at 90 DEG C and be cooled to room temperature, filter, obtain white crystal 152g after filtrate steaming removal solvent, yield 81.2%.The logical 848 potentiometric titrator chlorine detection content of Switzerland ten thousand are adopted to be that 3.1ppm, Shimadzu AA-6300 atomic absorption instrument detects sodium ion potassium ion 0.3ppm.Detect, at 1401cm through fourier infrared
-1, 1386cm
-1, 1190cm
-1, 1225cm
-1, 859cm
-1, 845cm
-1, 783cm
-1, 747cm
-1, by two fluoro sulfimide standard spectrogram contrast, be defined as the characteristic group of two fluoro sulfimide.
embodiment 6
220.0g(1mol is added under nitrogen protection in 1000ml there-necked flask) two chlorosulfonyl imine lithium; the two trifluoroethyl carbonic ether of 200.0g and 200.0g methylcarbonate; 232.0g (4mol) Potassium monofluoride, 26.1g (1mol) lithium fluoride and 18g18-are preced with-6-ether and 6g12-is preced with-4-ether.Under agitation, react after 24 hours at 90 DEG C and be cooled to room temperature, filter, obtain white crystal 151g after filtrate steaming removal solvent, yield 80.7%.The logical 848 potentiometric titrator chlorine detection content of Switzerland ten thousand are adopted to be that 3.1ppm, Shimadzu AA-6300 atomic absorption instrument detects sodium ion potassium ion 0.3ppm.Detect, at 1401cm through fourier infrared
-1, 1386cm
-1, 1190cm
-1, 1225cm
-1, 859cm
-1, 845cm
-1, 783cm
-1, 747cm
-1, by two fluoro sulfimide standard spectrogram contrast, be defined as the characteristic group of two fluoro sulfimide.
Comparative example:
US Patent No. 7253317 synthesizes two fluoro sulfimide alkali metal salt with alkaline metal fluoride cpd and two chlorosulfonyl imines in Nitromethane 99Min., and specific examples is:
1. by 3.556g(137.1mmol) lithium fluoride joins in 5ml Nitromethane 99Min., 4.907g(22.9mmol) two chlorosulfonyl imines is dissolved in 5ml Nitromethane 99Min., stirs to drip two chlorosulfonyl imines nitromethane solution down, drip to terminate rear reaction and spend the night.Get supernatant liquid and do nuclear magnetic resonance spectroscopy:
| Chemical shift | Peak height | Material type |
| 56.6 | 1 | FSO 2NH 2 |
| 50.8 | 78.4 | (SO 2F)(SO 2Cl)NH |
| 54.5 | 12.7 | SO 2F |
| 35.3 | 53.3 | FSO 3 - |
Find that it does not obtain two fluoro sulfimide lithium.
2. by 4.421g(29.1mmol) cesium fluoride joins in 2ml Nitromethane 99Min., 2.243g(10.48mmol) two chlorosulfonyl imines is dissolved in 5ml Nitromethane 99Min., stirs to drip two chlorosulfonyl imines nitromethane solution down, drip and terminate rear reaction 72 hours.Get supernatant liquid and do nuclear magnetic resonance spectroscopy:
| Chemical shift | Peak height | Material type |
| 56.5 | 15.5 | FSO 2NH 2 |
| 52.1 | 48.3 | (SO 2F)(SO 2Cl)N - |
| 51.9 | 225.6 | (SO 2F) 2N - |
About there are two chlorosulfonyl imines of 77.8% to start to change into two fluoro sulfimide by the display of nucleus magnetic resonance peak height, but do not obtain solid-state two fluoro sulfimide cesium salts.
Should be appreciated that, after having read above-mentioned teachings of the present invention, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
Claims (8)
1. the preparation method of a two fluoro sulfimide lithium, described method comprises: in unsaturated carbonate alkyl ester and/or saturated fluoro alkyl carbonate solvent, under the catalytic condition of the crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd, two chlorosulfonyl imine lithium is reacted with the alkaline metal fluoride cpd as fluorizating agent, obtains two fluoro sulfimide lithium.
2. the preparation method of two fluoro sulfimide lithium as claimed in claim 1, is characterized in that: the structural formula of described pair of chlorosulfonyl imine lithium is:
The structural formula of described pair of fluoro sulfimide lithium is:
3. the preparation method of two fluoro sulfimide lithium as claimed in claim 1, it is characterized in that: described alkaline metal fluoride cpd is selected from lithium fluoride, Potassium monofluoride, Sodium Fluoride or their mixture, the add-on of this alkaline metal fluoride cpd is 2.01 ~ 10 times of two chlorosulfonyl imine lithium mole number.
4. the preparation method of two fluoro sulfimide lithium as described in claim 1 or 3, it is characterized in that: described unsaturated carbonate alkyl ester solvents be selected from methylcarbonate, diethyl carbonate, dipropyl carbonate, Methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, in one or more mixture, its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium massfraction.
5. the preparation method of the two fluoro sulfimide lithium as described in claim 1 or 3, it is characterized in that: described saturated fluoro alkyl carbonate solvent is selected from one or more the mixture in trifluoroethyl ethyl carbonate ester, two trifluoroethyl carbonic ether, trifluoroethyl methyl carbonic, its add-on is 1 ~ 10 times of two chlorosulfonyl imine lithium mass fraction.
6. the preparation method of two fluoro sulfimide lithium as claimed in claim 1, is characterized in that: the described crown ether-like phase transfer catalysts adapted with alkaline metal fluoride cpd is 12-crown-4,15-be preced with-5 or 18-be preced with-6.
7. the preparation method of the two fluoro sulfimide lithium as described in claim 1 or 5, is characterized in that: the add-on of crown ether-like phase transfer catalysts is 0.1% ~ 10% of two chlorosulfonyl imine lithium massfraction.
8. the preparation method of two fluoro sulfimide lithium as claimed in claim 1, it is characterized in that: react and carry out at the temperature of 40 ~ 130 DEG C, the reaction times is 8 ~ 24 hours.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210331995.0A CN103663393B (en) | 2012-09-10 | 2012-09-10 | The preparation method of two fluoro sulfimide lithium |
| EP13835371.9A EP2894146B1 (en) | 2012-09-10 | 2013-02-26 | Method for preparing bis(fluorosulfonyl)imide |
| PL13835371T PL2894146T3 (en) | 2012-09-10 | 2013-02-26 | Method for preparing bis(fluorosulfonyl)imide |
| PCT/CN2013/071868 WO2014036814A1 (en) | 2012-09-10 | 2013-02-26 | Method for preparing bis(fluorosulfonyl)imide |
| KR1020157005898A KR101668293B1 (en) | 2012-09-10 | 2013-02-26 | Method for preparing bis(fluorosulfonyl)imide |
| HUE13835371A HUE041978T2 (en) | 2012-09-10 | 2013-02-26 | Method for preparing bis(fluorosulfonyl)imide |
| JP2015530266A JP5974181B2 (en) | 2012-09-10 | 2013-02-26 | Method for producing lithium bis (fluorosulfonyl) imide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210331995.0A CN103663393B (en) | 2012-09-10 | 2012-09-10 | The preparation method of two fluoro sulfimide lithium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103663393A CN103663393A (en) | 2014-03-26 |
| CN103663393B true CN103663393B (en) | 2015-09-30 |
Family
ID=50236495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210331995.0A Active CN103663393B (en) | 2012-09-10 | 2012-09-10 | The preparation method of two fluoro sulfimide lithium |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2894146B1 (en) |
| JP (1) | JP5974181B2 (en) |
| KR (1) | KR101668293B1 (en) |
| CN (1) | CN103663393B (en) |
| HU (1) | HUE041978T2 (en) |
| PL (1) | PL2894146T3 (en) |
| WO (1) | WO2014036814A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102542990B1 (en) * | 2015-06-23 | 2023-06-12 | 가부시기가이샤 닛뽕쇼꾸바이 | Conductive material, manufacturing method and purification method thereof, and non-aqueous electrolyte and antistatic agent using the conductive material |
| KR101718292B1 (en) * | 2015-11-26 | 2017-03-21 | 임광민 | Novel method for preparing lithium bis(fluorosulfonyl)imide |
| CN105731398B (en) * | 2016-01-25 | 2018-01-23 | 苏州氟特电池材料股份有限公司 | A kind of preparation method of the alkali metal salt of double fluorine sulfimides |
| CN107226461B (en) * | 2016-03-25 | 2020-12-18 | 浙江省化工研究院有限公司 | Preparation method of bis (fluorosulfonyl) imide salt |
| CN105947998B (en) * | 2016-04-29 | 2018-05-15 | 金国范 | A kind of method that imidodisulfuryl fluoride lithium salt is prepared using lithium nitride |
| WO2017204303A1 (en) * | 2016-05-27 | 2017-11-30 | 株式会社日本触媒 | Method for producing bis(fluorosulfonyl)imide alkali metal salt |
| CN106219503B (en) * | 2016-07-12 | 2018-11-30 | 武汉松石科技股份有限公司 | It is a kind of double（Fluorine sulphonyl）The preparation method of imines and its alkali metal salt |
| CN108147981B (en) * | 2016-12-06 | 2020-05-22 | 中国科学院宁波材料技术与工程研究所 | Method for preparing sulfimide compound by reverse phase transfer catalysis |
| KR101926856B1 (en) * | 2017-03-22 | 2018-12-10 | 제이투에이치바이오텍 (주) | Method for preparing extrapure fluorosulfonylimide with removing methallic cation |
| KR101955096B1 (en) * | 2017-06-26 | 2019-03-06 | 임광민 | Novel preparing method of very efficient and simple lithium bis(fluorosulfonyl)imide |
| CN107651654A (en) * | 2017-10-27 | 2018-02-02 | 江苏理文化工有限公司 | A kind of preparation method of double fluorine sulfimide lithiums using villiaumite as fluorization agent |
| CN109721037B (en) | 2019-03-11 | 2019-12-24 | 上海如鲲新材料有限公司 | Novel process of bis (fluorosulfonyl) imide salt |
| JP7288776B2 (en) * | 2019-03-19 | 2023-06-08 | 国立大学法人 東京大学 | Aqueous electrolyte for power storage device and power storage device containing this water-based electrolyte |
| JP7288775B2 (en) * | 2019-03-19 | 2023-06-08 | 国立大学法人 東京大学 | Aqueous electrolyte for power storage device and power storage device containing this water-based electrolyte |
| JP7288777B2 (en) * | 2019-03-19 | 2023-06-08 | 国立大学法人 東京大学 | Aqueous electrolyte for power storage device and power storage device containing this water-based electrolyte |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| CN111320151A (en) * | 2020-02-18 | 2020-06-23 | 白银科奥夫化学科技有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2527802A1 (en) * | 2005-12-12 | 2007-06-12 | Christophe Michot | Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent |
| CN102046523A (en) * | 2008-07-23 | 2011-05-04 | 第一工业制药株式会社 | Process for producing bis(fluorosulfonyl)imide anion compound, and ion-pair compound |
| CN102405189A (en) * | 2009-11-27 | 2012-04-04 | 株式会社日本触媒 | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
| CN102617414A (en) * | 2012-03-02 | 2012-08-01 | 苏州氟特电池材料有限公司 | Synthesis methods of alkali metal salt containing sulfonyl chloride or phosphorus imide and alkali metal salt containing fluorine sulfonyl or phosphorus imide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2818972B1 (en) * | 2000-12-29 | 2003-03-21 | Rhodia Chimie Sa | PROCESS FOR FLUORINATION OF A HALOGEN COMPOUND |
| US8134027B2 (en) * | 2008-03-31 | 2012-03-13 | Nippon Shokubai Co., Ltd. | Sulfonylimide salt and method for producing the same |
| EP3736250B1 (en) * | 2010-05-28 | 2023-07-26 | Nippon Shokubai Co., Ltd. | Alkali metal salt of fluorosulfonyl imide |
-
2012
- 2012-09-10 CN CN201210331995.0A patent/CN103663393B/en active Active
-
2013
- 2013-02-26 EP EP13835371.9A patent/EP2894146B1/en active Active
- 2013-02-26 PL PL13835371T patent/PL2894146T3/en unknown
- 2013-02-26 KR KR1020157005898A patent/KR101668293B1/en active IP Right Grant
- 2013-02-26 WO PCT/CN2013/071868 patent/WO2014036814A1/en unknown
- 2013-02-26 JP JP2015530266A patent/JP5974181B2/en active Active
- 2013-02-26 HU HUE13835371A patent/HUE041978T2/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2527802A1 (en) * | 2005-12-12 | 2007-06-12 | Christophe Michot | Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent |
| CN102046523A (en) * | 2008-07-23 | 2011-05-04 | 第一工业制药株式会社 | Process for producing bis(fluorosulfonyl)imide anion compound, and ion-pair compound |
| CN102405189A (en) * | 2009-11-27 | 2012-04-04 | 株式会社日本触媒 | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
| CN102617414A (en) * | 2012-03-02 | 2012-08-01 | 苏州氟特电池材料有限公司 | Synthesis methods of alkali metal salt containing sulfonyl chloride or phosphorus imide and alkali metal salt containing fluorine sulfonyl or phosphorus imide |
Also Published As
| Publication number | Publication date |
|---|---|
| PL2894146T3 (en) | 2019-02-28 |
| EP2894146A4 (en) | 2016-04-27 |
| EP2894146B1 (en) | 2018-08-22 |
| JP2015535789A (en) | 2015-12-17 |
| WO2014036814A1 (en) | 2014-03-13 |
| KR20150039845A (en) | 2015-04-13 |
| EP2894146A1 (en) | 2015-07-15 |
| CN103663393A (en) | 2014-03-26 |
| HUE041978T2 (en) | 2019-06-28 |
| JP5974181B2 (en) | 2016-08-23 |
| KR101668293B1 (en) | 2016-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663393B (en) | The preparation method of two fluoro sulfimide lithium | |
| EP3466871B1 (en) | Method for producing bis(fluorosulfonyl)imide alkali metal salt and bis(fluorosulfonyl)imide alkali metal salt composition | |
| CN110233289B (en) | High-voltage additive, electrolyte containing same and battery | |
| JP5315971B2 (en) | Method for producing difluorobis (oxalato) lithium phosphate solution | |
| CN107226821B (en) | A kind of synthesis technology preparing difluorine oxalic acid boracic acid lithium with di-oxalate lithium borate | |
| JP2014533293A (en) | Method for producing metal difluorochelate borate and use as battery electrolyte or additive in galvanic cells | |
| CN102473964A (en) | Asymmetric and/or low-symmetry fluorine-containing phosphate ester for use in a nonaqueous electrolyte solution | |
| CN104671224B (en) | The synthetic method of double fluorine sulfimide salt | |
| CN111517293B (en) | Preparation method of bis-fluorosulfonyl imide compound and metal salt thereof | |
| WO2012069554A1 (en) | Process for preparing organic lithium salts | |
| CN109836444A (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| CN109850926B (en) | Preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate | |
| CN109678694A (en) | A kind of preparation method of tetrafluoro oxalic acid lithium phosphate | |
| WO2016093400A1 (en) | Method for preparing lithium bis(fluorosulfonyl) imide salt and intermediate product obtained from the same | |
| CN105399761A (en) | Preparation method of lithium difluoro(oxalato)borate | |
| CN103429566B (en) | Method for preparing a dinitrile compound | |
| CN110343125A (en) | A kind of method and this application for mixing lithium salts in lithium ion battery of low cost preparation high-purity certainty ratio mixing lithium salts | |
| CN111137870B (en) | Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte | |
| CN113717205A (en) | Preparation method of lithium oxalate borate and derivatives thereof, electrolyte and secondary battery | |
| CN115676855A (en) | Preparation method of sodium ion battery electrolyte sodium salt | |
| CN111825704A (en) | Method for purifying lithium difluoro (oxalato) borate | |
| CN115477308A (en) | Method for preparing sodium tetrafluoroborate at normal temperature by one-step method | |
| CN110240610A (en) | A kind of preparation method of the double borate difluoroborates of polyalcohol | |
| CN117088390B (en) | Preparation method of hexafluorophosphate, electrolyte and secondary battery | |
| CN101550058A (en) | Method for refining overcharging additive biphenyl of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 215635 No. 28, Qinghai Road, Yangzi International Chemical Industrial Park, Zhangjiagang, Jiangsu, Jiangsu Patentee after: HSC Corporation Address before: 215635, No. 28, Qinghai Road, Yang Zijiang International Chemical Industrial Park, Jiangsu, Jiangsu, Suzhou, Zhangjiagang Patentee before: Jiangsu Huasheng Chemicals Co., Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No.10, Qinghai Road, Yangtze River International Chemical Industry Park, Suzhou, Jiangsu 215635 Patentee after: Jiangsu Huasheng lithium battery materials Co., Ltd Address before: 215635 No. 28, Qinghai Road, Yangzi International Chemical Industrial Park, Zhangjiagang, Jiangsu, Jiangsu Patentee before: HSC Corporation |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210517 Address after: 321200 new material industrial park, huchu Industrial Zone, Shuxi street, Wuyi County, Jinhua City, Zhejiang Province Patentee after: Zhejiang shengmei lithium battery materials Co.,Ltd. Address before: No.10, Qinghai Road, Yangzijiang International Chemical Industrial Park, Suzhou, Jiangsu, 215635 Patentee before: Jiangsu Huasheng lithium battery materials Co.,Ltd. |